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SURFACE CHEMISTRY
ADSORPTION
Introduction
Adsorption: Concentration or assimilation of a gas (or liquid) at the surface
of a solid (or liquid)
Occlusion. The adsorption of gases on the surface of solids
Adsorbent: The material providing the surface upon which adsorption
occurs
Adsorbate: The substance get adsorbed or attached on the surface of
adsorbent
Ex: Charcoal, Silica gel, Alumina gel, Clay, etc.
Desorption: The removal of adsorbed substance from the surface
Positive adsorption: Concentration of the adsorbate is more on the surface
of the adsorbent than in the solution (bulk).
e.g., In the concentrated solution of KCl, charcoal adsorbs KCl rather than
water and this leads decrease in concentration of KCl in solution.
Negative adsorption: Concentration of the adsorbate is less on the surface
of the adsorbent than in the solution (bulk)
e.g. In the dilute solutions of KCl, charcoal adsorbs water, thereby the salt
concentration is increased.
Adsorption Absorption
1. Concentration or assimilation of a 1. The substance assimilated is
gas (or a liquid) at the surface of a uniformly distributed throughout the
solid (or body of the solid
liquid) or liquid.
2. A surface phenomenon 2. A bulk phenomenon
3. A fast process 3. A slow process
4. Equilibrium is attained easily 4. Attainment of equilibrium takes
some time
CLASSIFICATION OF ADSORPTION
Based on the force of attraction
Physical adsorption (or physisorption) or van der Waals adsorption:
The adsorbed molecules are held to the surface of the adsorbent by weak
physical or van der Waal’s forces.
e.g: Adsorption of various gases by charcoal belongs to this type.
Chemical adsorption or chemisorption or activated adsorption:
The adsorbed molecules are held by chemical bonds.
e.g: Adsorption of oxygen on tungsten, and on charcoal.
Differences between Physical adsorption and Chemical adsorption
Physical adsorption Chemical adsorption
(Physisorption) (Chemisorption)
1. Heat of adsorption is about 20-40 Heat of adsorption is about 40-400
kcal/mol kcal/mol
2.Adsorption is completely Adsorption is irreversible, since
reversible, since the molecules are molecules are tightly retained by
not tightly retained by the adsorbent adsorbent
3. Adsorption is appreciable only at Adsorption can occur at high
temperature below the boiling point temperatures
of the adsorbate, and it decreases
with rise in temperature
4. Multilayer adsorption occurs, i.e., Adsorption leads to , utmost, a
adsorbed layer may be several monolayerForces
molecules thick, since the van der
Waal’s forces can extend from one
layer to another
5. Forces responsible for such responsible for such adsorption are
adsorption are very weak quite strong
6. The rate of adsorption increases The rate of adsorption decreases with
with the increase of pressure or the increase of pressure or
concentration of the adsorbate. Near concentration of the adsorbate. Near
saturation pressure, multilayers are saturation pressure, adsorption rate
formed decreases, since the adsorption is
confined only to upper surface layer
of adsorbent
7. The amount of adsorption on a The amount of adsorption is
surface is more function of the characteristicof both adsorbate and
adsorbate than the adsorbent adsorbent.
8. Such adsorption involves very Activation energy is involved in
small or little activation energy chemical bond formation
where
x = mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
c = Equilibrium concentration of adsorbate in solution.
K and 1/n are constants for a given adsorbate and adsorbent at a particular
temperature
Ion Exchange resins are insoluble cross linked long chain macro polymer
with micro porous structure and the functional groups attached to the chains
are responsible for the ion exchanging properties.
- + - +
SO3 H SO3 H
- + -
SO3 H +
SO3 H
Capable of exchanging their cations with other cations
Polymers containing acidic functional gps like sulphonic (-SO3H) and
carboxylic(-COOH) acids
Sulphonated is more acidic because its pKa = 1, so completely ionized when
in contact with water
Generally represented as R-H+
Exchange H+ ions with other cations
2R-H++ Ca+===== R2Ca+ + 2H+
Cation exchange reaction is reversible, the original resin can be
regenerated on treatment with acid
+ - + -
CH2 N(CH3)3 OH CH2 N(CH3)3 OH
+ - + -
CH2 N(CH3)3 OH CH2 N(CH3)3 OH
Capable of exchanging their anion OH- with other anions (Cl-, SO42-, etc,..).
Polymers containing basic functional gps like quaternary Ammonium
hydroxide and amino gps
Quaternary Ammonium hydroxide is more basic in nature, since its pKb =
14, so completely ionized when in contact with water
Generally represented as R+OH-
Exchange OH- ions with other anions
R+OH- + Cl- ===== R+Cl-+ OH-
Anion exchange reaction is reversible, the original resin can be
regenerated on treatment with base
Process:
The water coming out is completely free from cations and anions.
This water is known as DM water or deionised water.
Advantages
1. This process can be used to soften highly acidic or alkaline
waters
2. It produces water of very low hardness (2 ppm)
Disadvantages
1. This equipment is costly and more expensive chemicals are
needed.
2. Turbid water clogs the pores in the ion –exchange bed, so turbid
water cannot be used. Turbidity should be lower than 10 ppm
2. Zeolite process
REFER NOTES:
ZeNa2 + Ca2+
- ZeCa + 2Na+
Adsorption Chromatography
Based on the differences in the adsorption coefficients of substances on
solid
The mobile phase is allowed pass through the stationary phase. The
stationary phase retains the components of mobile phase at different points
depends on their adsorption.
Stationary phase:
Adsorbent packed in the column. Ex: silica gel, alumina.
Mobile phase:
The mixture of components is allowed to flow slowly over the stationary
phase.
Process
StepI: Separation of various compounds
The components with higher adsorption tend to be retained at the top, the
other components are adsorbed successively at various distance depends on
their adsorption.
A number of horizontal bands or zones or rings of different colours are
produced in the column. The colored zones or banded column of the
adsorbed substance is called as Chromatogram.
StepII: Identification of compounds
The various zones are dissolved separately in suitable solvents and estimated
The process of recovery of various substances is elution and the solvent is
called eluent.
Advantage
1. Separation of a mixture of molecules with similar chemical properties and
almost equal boiling points is possible only in adsorption chromatography
2. Large volume of samples can be separated.
Applications
1. Quantitative separation of two or more substances.
2. Purification of organic substances
ACTIVATED CARBON
Among the various adsorbents, in treatment of polluted water and air ,
the activated carbon is the most commonly used adsorbent because of
its porous structure with high surface area per unit mass
The S.A of A.C = 1000 m2 / g
It was first used as an adsorbent in gas masks in World War I.
Preparation
1. Preparation Char (carbon) form raw materials
The char is produced by heating (carbonizing) the raw materials like
coconut, wood, coal, petroleum residues, saw dust , lignite to red heat in
a retart to remove hydrocarbons in insufficient supply of air
2. Activation of carbon
1) Direct Process: Heating carbon at 850C in a current of superheated steam
2) Briquetting process: Powdered carbon is mixed with wood, tar and
caustic soda, compressed in small briquettes and then heated in steam at
800C.
3) Chemical Process: Wood is impregnated with the solution of zinc
chloride or phosphoric acid and then carbonized.
Classification of Activated Carbon
1)Granular Activated Carbon(GAC)
Diameter of greater than 0.1nm
Used for adsorption of gases, vapors and solute particles
Produced from coconut shells, fruit pits, charcoal and briquetted coal
2) Powder Activated Carbons(PAC)
Diameter of less than 200mesh
Used in purification of liquids
Saw dust and lignite are raw materials
Properties
Activated carbon has enormous surface area of the order of 1000 m2/ g.
Activated carbon is able to adsorb practically any volatile organic
compounds (VOC) at lower temperature (35oC) and can be released on
heating to a higher temperature (120o C).
II. In abatement of water or air pollution
The fresh water available on the earth is only 2%. Hence proper
maintenance, conservation and use of water resources are required to avoid
chances of water scarcity for future generation. It is therefore necessary to
treat water and reuse wastewater, so as to increase and improve the quality
of water and make it for use.
Activated carbon is used in water treatment process.
Theory:
*It is both hydrophobic and oleophilic (ie) it hates water but has affinity for
oil and other organic chemicals since A.C adsorbs preferably non-electrolyte
than electrolyte.
*When the flow condition is suitable, dissolved chemicals in water flowing
over the surface of carbon get adsorbed on the surface while the water passes
over.
*Activated carbons used in waste water treatment are Granular Activated
carbon (GAC) and powdered Activated carbon (PAC).
1. Using GAC
GAC is used because of its porous structure and high surface area. It is
cheaper, effective and can be reused.
Water treatment can be done by using two different type of fiixed bed
columns as follow,
1. Up flow fixed bed A.C contactors:
2. Down flow fixed bed A.C contactors
3. Advantages
4. Disadvantages
REFERBOOK
2. Using PAC
Biologically treated water -- mixed with PAC --- allowed for adsorption
-- sedimentation with coagulants like poly electrolyte (Polyelectrolytes are
polymers whose repeating units bear an electrolyte group. These groups will
dissociate in aqueous solutions (water), making the polymers charged. Ex:
Poly(acrylic acid) PAA will lose their protons and acquire a negative charge
and poly(sodium styrene sulfonate). --filteration using GAC bed and sand
filter -- pure water
Regeneration
Activated carbon is able to adsorb organic compounds (VOC) at lower
temperature (35oC) and can be released on heating to a higher temperature
(120o C).
GAC’s can be regenerated in a furnace by heating it in the presence of
limited amount of super heated steam, flue gas and oxygen. Some carbon (5
- 10%) is destroyed during regeneration process
ROLE OF ADSORPENTS
In Catalytic Reaction: Heterogeneous catalysis
Heterogeneous catalysis
This involves the use of a catalyst in a different phase from the reactants.
Typical examples involve a solid catalyst with the reactants as either liquids
or gases.
One or more of the reactants are adsorbed on to the surface of the catalyst at
active sites. An active site is a part of the surface which is particularly good
at adsorbing things and helping them to react.
There is some sort of interaction between the surface of the catalyst and the
reactant molecules which makes them more reactive.
This might involve an actual reaction with the surface, or some weakening
of the bonds in the attached molecules.
At this stage, both of the reactant molecules might be attached to the surface,
or one might be attached and hit by the other one moving freely in the gas or
liquid.
Desorption simply means that the product molecules break away. This
leaves the active site available for a new set of molecules to attach to and
react.
A good catalyst needs to adsorb the reactant molecules strongly enough for
them to react, but not so strongly that the product molecules stick more or
less permanently to the surface.
Silver, for example, isn't a good catalyst because it doesn't form strong
enough attachments with reactant molecules. Tungsten, on the other hand,
isn't a good catalyst because it adsorbs too strongly.
Metals like platinum and nickel make good catalysts because they adsorb
strongly enough to hold and activate the reactants, but not so strongly that
the products can't break away.
Examples of heterogeneous catalysis
The simplest example of this is the reaction between ethene and hydrogen in
the presence of a nickel catalyst.
Ethene molecules are adsorbed on the surface of the nickel. The double bond
between the carbon atoms breaks and the electrons are used to bond it to the
nickel surface.
Hydrogen molecules are also adsorbed on to the surface of the nickel. When this
happens, the hydrogen molecules are broken into atoms. These can move around
on the surface of the nickel.
If a hydrogen atom diffuses close to one of the bonded carbons, the bond
between the carbon and the nickel is replaced by one between the carbon and
hydrogen.
That end of the original ethene now breaks free of the surface, and eventually
the same thing will happen at the other end.
As before, one of the hydrogen atoms forms a bond with the carbon, and that
end also breaks free. There is now space on the surface of the nickel for new
reactant molecules to go through the whole process again.